The development of new heterostructures with high photoactivity is a breakthrough for the limitation of solar-driven water splitting.Here,we first introduce indium oxide(In_(2)O_(3))nanorods(NRs)as a novel electron tr...The development of new heterostructures with high photoactivity is a breakthrough for the limitation of solar-driven water splitting.Here,we first introduce indium oxide(In_(2)O_(3))nanorods(NRs)as a novel electron transport layer for bismuth vanadate(BiVO_(4))with a short charge diffusion length.In_(2)O_(3)NRs reinforce the electron transport and hole blocking of BiVO_(4),surpassing the state-of-the-art photoelectrochemical performances of BiVO_(4)-based photoanodes.Also,a tannin-nickel-iron complex(TANF)is used as an oxygen evolution catalyst to speed up the reaction kinetics.The final TANF/BiVO_(4)/In_(2)O_(3)NR photoanode generates photocurrent densities of 7.1 mAcm^(−2) in sulfite oxidation and 4.2 mA cm^(−2) in water oxidation at 1.23 V versus the reversible hydrogen electrode.Furthermore,the“artificial leaf,”which is a tandem cell with a perovskite/silicon solar cell,shows a solar-to-hydrogen conversion efficiency of 6.2%for unbiased solar water splitting.We reveal significant advances in the photoactivity of TANF/BiVO_(4)/In_(2)O_(3)NRs from the tailored nanostructure and band structure for charge dynamics.展开更多
Although bismuth vanadate(BiVO4)has been promising as photoanode material for photoelectrochemical water splitting,its charge recombination issue by short charge diffusion length has led to various studies about heter...Although bismuth vanadate(BiVO4)has been promising as photoanode material for photoelectrochemical water splitting,its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes.As a hole blocking layer of BiVO4,titanium dioxide(TiO_(2)) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity.Herein,a crystal facet engineering of TiO_(2) nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots.We design two types of TiO_(2) nanostructures,which are nanorods(NRs)and nanoflowers(NFs)with different(001)and(110)crystal facets,respectively,and fabricate BiVO4/TiO_(2) heterostructure photoanodes.The BiVO4/TiO_(2) NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO_(2) NRs.Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination,which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO_(2) NFs.This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.展开更多
基金National Research Foundation of Korea,Grant/Award Numbers:2021M3H4A1A03057403,2021R1A6A3A03039988,2021R1A6A3A13046700,2021R1A2B5B03001851。
文摘The development of new heterostructures with high photoactivity is a breakthrough for the limitation of solar-driven water splitting.Here,we first introduce indium oxide(In_(2)O_(3))nanorods(NRs)as a novel electron transport layer for bismuth vanadate(BiVO_(4))with a short charge diffusion length.In_(2)O_(3)NRs reinforce the electron transport and hole blocking of BiVO_(4),surpassing the state-of-the-art photoelectrochemical performances of BiVO_(4)-based photoanodes.Also,a tannin-nickel-iron complex(TANF)is used as an oxygen evolution catalyst to speed up the reaction kinetics.The final TANF/BiVO_(4)/In_(2)O_(3)NR photoanode generates photocurrent densities of 7.1 mAcm^(−2) in sulfite oxidation and 4.2 mA cm^(−2) in water oxidation at 1.23 V versus the reversible hydrogen electrode.Furthermore,the“artificial leaf,”which is a tandem cell with a perovskite/silicon solar cell,shows a solar-to-hydrogen conversion efficiency of 6.2%for unbiased solar water splitting.We reveal significant advances in the photoactivity of TANF/BiVO_(4)/In_(2)O_(3)NRs from the tailored nanostructure and band structure for charge dynamics.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)(2021R1A2B5B03001851)the NRF Grant funded by the Korean government MSIT(2021M3H4A1A03057403).M.G.L.acknowledges the Basic Science Research Program through the NRF funded by the Ministry of Education(2021R1A6A3A03039988).J.W.Y.acknowledges the Basic Science Research Program through the NRF funded by the Ministry of Education(2021R1A6A3A13046700).
文摘Although bismuth vanadate(BiVO4)has been promising as photoanode material for photoelectrochemical water splitting,its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes.As a hole blocking layer of BiVO4,titanium dioxide(TiO_(2)) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity.Herein,a crystal facet engineering of TiO_(2) nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots.We design two types of TiO_(2) nanostructures,which are nanorods(NRs)and nanoflowers(NFs)with different(001)and(110)crystal facets,respectively,and fabricate BiVO4/TiO_(2) heterostructure photoanodes.The BiVO4/TiO_(2) NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO_(2) NRs.Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination,which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO_(2) NFs.This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.
